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1.
A method is described to estimate the chemical form of gold (Au) in a variety of geological reference samples, combining a sequential extraction scheme with graphite furnace atomic absorption spectrometry, after extraction of Au as iodide or chloride with methyl isobutyl ketone. The fractions dissolved by sequential extraction are empirically defined as the exchangeable, amorphous, metallic, aqua regia-soluble and residual fractions. The amounts of Au in the amorphous fraction have been derived mainly from oxide or amorphous phases, and the chemical forms of Au are considered to be mostly amorphous and partly metallic. The metallic fraction of Au is likely to exist as submicroscopic grains of native metal which are relatively free from the rock-forming minerals, whereas the aqua regia-soluble or residual fraction of Au may be bound more intimately perhaps as inclusions or solid solutions of either native metal or electrum in most cases. Satisfactory agreement was observed between the sum of the Au values from exchangeable to residual fractions and the reported total Au values, except for a few samples which contained a large amount of reducing materials. Analytical results of Au for twenty six geological reference materials are tabulated, and geochemical and mineralogical features are discussed.  相似文献   

2.
Arsenic and antimony contamination is found at the Pezinok mining site in the southwest of the Slovak Republic. Investigation of this site included sampling and analysis of water, mineralogical analyses, sequential extraction, in addition to flow and geochemical modeling. The highest dissolved arsenic concentrations correspond to mine tailings (up to 90,000 μg/L) and the arsenic is present predominately as As(V). The primary source of the arsenic is the dissolution of arsenopyrite. Concentration of antimony reaches 7,500 μg/L and its primary source is the dissolution of stibnite. Pore water in mine tailings is well-buffered by the dissolution of carbonates (pH values between 6.6 and 7.0) and arsenopyrite grains are surrounded by reaction rims composed of ferric iron minerals. Based on sequential extraction results, most solid phase arsenic is in the reducible fraction (i.e. ferric oxyhydroxides), sulfidic fraction, and residual fraction. Distribution of antimony in the solid phase is similar, but contents are lower. The principal attenuation mechanism for As(V) is adsorption to ferric oxide and hydroxides, but the adsorption seems to be limited by the competition with Sb(V) produced by the oxidation of stibnite for adsorption sites. Water in mine tailings is at equilibrium with gypsum and calcite, but far from equilibrium with any arsenic and antimony minerals. The concentrations of arsenic and antimony in the surrounding aquifer are much lower, with maximum values of 215 and 426 μg/L, respectively. Arsenic and antimony are transported by ground water flow towards the Blatina Creek, but their loading from ground water to the creek is much lower compared with the input from the mine adits. In the Blatina Creek, arsenic and antimony are attenuated by dilution and by adsorption on ferric iron minerals in stream sediments with resulting respective concentrations of 93 and 45 μg/L at the site boundary south of mine tailing ponds.  相似文献   

3.
A five step sequential extraction technique, following Tessier’s protocol has been applied to determine the chemical association of aluminium with major sedimentary phases (exchangeable, carbonate, manganese and iron oxides, organic and residual fraction) in four short sediment cores collected from El-Burullus lagoon of the Nile delta, Egypt. This study is a first approach of chemical fractionation of aluminium in one of the protective areas of the Mediterranean Sea of Egypt. The total metal content was also determined. The results of the fractionation study indicated that aluminium was mainly associated with the residual fraction (>95%). The organic and Fe–Mn oxide fractions were the next important phases. The exchangeable and carbonate fractions were less than 1%, limiting its potential toxicity as a pollutant. The geochemical analysis of aluminium forms reflected the lithogenic origin of this metal in the study area.  相似文献   

4.
Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO3), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.  相似文献   

5.
云浮黄铁矿利用过程中微量毒害元素的环境化学活动性   总被引：13，自引：3，他引：13  
为了解云浮黄铁矿利用过程中微量毒害元素的环境地球化学行为，客观评价它们对环境质量的影响，利用元素结合形态的连续提取实验方法，分析了云浮黄铁矿及其工业废渣中Co,Ni,Cu,Zn,As,Se,Cd,Sn,Sb,Pb和Tl等11种毒害元素的形态及化学活动性。结果表明，黄铁矿中大部分微量毒害元素都有着极强的化学活动性，各元素活动态浸出比例依次为Co96.3%,Se91.9%,Cu90.3%,Cd90.0%,Pb89.7%,Zn88.6%,Sb82.5%,Ni80.6%，Sn70%,Tl55.1%和As31.9％，元素As和Tl主要赋存于硫化物和硅酸盐矿物相中，另有少量的Cu,Pb和Sb可能赋存于碳酸盐矿物相中，其他元素则主要赋存于硫化物矿物相中。与黄铁矿相比，飞灰和灰渣中各元素可交换态和碳酸盐结合态所占的比例明显减少。废渣中各元素的化学活动性表现出很大的差别，其中Cu,Zn和Cd的化学活动性最强，活性态浸出比例在90％以上；其次是Co,Ni,Se,Pb和Tl，浸出比例在50％左右；Sb,As和Sn的稳定性较高，浸出比例分别为1％、5％和14％左右；飞灰中微量毒害元素的活动性均高于灰渣。  相似文献   

6.
A field study was conducted to clarify the effect of rhizosphere processes on the accumulation and partitioning of heavy metals (Pb, Zn, Cu, Cr, Cd and Ni) in mangrove sediments. Metals were fractionated by a sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe–Mn oxide bound (B2), and organic and sulfide bound (B3). Results indicate that rhizosphere processes tend to increase the metal concentrations in the rhizosphere sediments. However, plant uptake may result in the decrease of the metal concentrations in the rhizosphere sediments when the metal concentrations are relatively low in the bulk sediments. Compared with the bulk sediments, the rhizosphere sediments have low concentrations of heavy metals in the B1 and B2 fractions and high concentrations in the B3 fraction. Either an increase or decrease in the residual fraction of heavy metals in the rhizosphere sediments may appear, depending on whether the formation of the refractory metal-organic compounds or the activation of the residual fractions dominates. Results also indicate that mangrove plants absorb and store non-essential metals in the perennial tissues, thus reducing the export of non-essential metals via leaf litter transport. Mangrove plants are excellent candidates for phytostabilization of heavy metals in intertidal substrates.  相似文献   

7.
Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.  相似文献   

8.
北京市街道灰尘中重金属元素赋存状态及环境效应   总被引：5，自引：3，他引：2  
刘春华  岑况  于扬 《岩矿测试》2011,30(2):205-209
采用Tessier的五步提取法,对北京北西—南东剖面所采集的街道灰尘样品粒度≤100μm组分中As、Cd、Cr、Hg、Pb和Zn等6元素的5个形态(可交换态、碳酸盐结合态、铁锰氧化物结合态、有机物结合态、残渣态)的分布特征研究发现,在可交换态和碳酸盐结合态中Cd的含量比都为最高,Pb、Hg、Zn和As在有机物结合态中含量比相近,铁锰氧化物结合态中Pb所占比例最高,而As和Cr主要存在于残渣态中。6种街道灰尘污染元素的相对活动性和潜在生物利用度顺序为:Cd>Zn>Pb>Cr>Hg>As。  相似文献   

9.
Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).  相似文献   

10.
The speciation of heavy metals such as thallium, cadmium and lead existing in pyrite and pyrite cinder was analyzed by ICP-MS with a sequential extraction procedure. The distribution patterns of these metals including exchangeable, reducible, oxidizable and residual fractions were obtained. Tl, Cd and Pb in pyrite and pyrite cinder samples from each extraction step were determined by inductively coupled plasma mass spectrometry (ICP-MS). Under the optimized instrumental conditions, detection limits of Tl, Cd and Pb in different matrices were within the range of 0.006–0.07 μg/L, and the relative standard deviations ranged from 0.8% to 1.2%. The accuracy of Tl, Cd and Pb determination was checked by analyzing two certified reference materials. The results demonstrate that trace Tl, Cd and Pb in the samples can be accurately determined. The sequential extraction results revealed that the percent contents of Tl, Cd and Pb in exchangeable, reducible and oxidizable fractions in pyrite cinder are different from those in pyrite and in pyrite cinder. Tl, Cd and Pb mostly are distributed in residual fraction. Therefore, the mobility of metals in pyrite is higher than that in pyrite cinder. Although distributions of Tl, Cd and Pb in the non-residual fraction are not dominant in pyrite cinder, the total concentrations of them could not be ignored. Consequently, attention must be paid to the risk of potential pollution by pyrite cinder.  相似文献   

11.
Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.  相似文献   

12.
Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As3+ vs. As5+), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg−1, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As3+ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO4 reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As3+ and presence of As5+ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.  相似文献   

13.
高硒环境样品中硒的形态分析方法   总被引：2，自引：0，他引：2  
在恩施富硒碳质岩和土壤样品中硒矿物学研究的基础上,提出了硒连续化学提取的改进方案。化学操作上定义为7个连续步骤:水溶态(MQ水提取)、可交换态(0.1 mol/L的K2HPO4 KH2PO4,pH=7.0)、有机结合态(0.1 mol/L NaOH)、元素态(1 mol/L Na2SO3溶液)、酸溶性提取态(15%CH3CO2H溶液)、硫化物/硒化物态(1 mol/L CrCl2 HCl溶液)和残渣态硒(HNO3 HF H2O2混合消化液)。使用HG-AFS法检测了各结合态中的硒形态和总硒,上述流程提取硒加和与总硒间显著一致,平均回收率为99.2%,符合平行样品间变异系数低于10%的精度要求。该方法简单易行,能够准确地揭示富硒地质样品中硒的形态信息。  相似文献   

14.
A laboratory study was conducted to evaluate the influence of hydration and recarbonation on the solidphase distribution of trace elements in retorted oil shale. The oil shale samples were retorted by the Paraho direct heating process and equilibrated with deionized—distilled water under controlled carbon dioxide conditions. A sequential extraction technique was then used to fractionate trace elements into soluble, KNO3-extractable (easily exchangeable), H2O-extractable (easily adsorbed), NaOh-extractable (organic), EDTA-extractable (carbonate), HNO3-extractable (sulfide), and residual (nonextractable silicate) phases. The chemical fractions present in retorted oil shale and hydrated and recarbonated retorted oil shale were compared to identify trace element mineralogical changes that may occur in retorted oil shale disposal environments.Trace elements examined in this study were found to reside predominantly in the HNO3-extractable and residual fractions. Hydration of retorted oil shale resulted in a shift in the majority of trace elements from residual to extractable forms. Cobalt, nickel, and zinc extractabilities were not significantly influenced by hydration, whereas antimony increased in the residual fraction. Subjecting retorted oil shale to atmospheric (0.033%) and 10% CO2(g) levels over a nine-month equilibration period resulted in partial and full recarbonation, respectively. As the influence of recarbonation increased, trace elements reverted to residual forms. Vanadium, choromium, copper, zinc, antimony, and molybdenum in the 10% CO2(g) recarbonated material were more resistant to sequential extraction than in retorted oil shale, whereas strontium, barium, and manganese were less resistant to sequential extraction. The extractabilities of cobalt, nickel, and lead were not affected by recarbonation. Recarbonation did not result in a predicted increase in EDTA-extractable trace elements. In general, the amounts of trace elements extracted by EDTA (and correlated to carbonate forms) were invariant with respect to equilibrium CO2(g) levels.A significant result of this study was that the mineralogical residencies of trace elements in retorted oil shale were altered in response to conditions that may be present in a disposal environment. Thus, the long-term release of trace elements in retorted oil shale disposal environments may not be adequately predicted by applying the toxicity characteristic leaching procedure (TCLP).  相似文献   

15.
本文研究地质样品中铀形态的分析方法及应用技术,以进一步说明铀形态分析在地球化学找矿中的重要作用。该方法参考Tessier流程,将样品中的铀分为可交换离子态、碳酸盐结合态、铁锰氧化物结合态、硫化物及有机物结合态和结晶态,分别提取,提取溶液用高分辨率电感耦合等离子体质谱仪进行测量。设计的形态提取配方具有良好的可选择性和可重复性,经过国家标准物质、国际形态标准物质和人工模拟样品验证,证明形态提取试剂配方适合所定义的形态分析。通过对实际样品(总量铀为635μg/g)验证表明,碳酸盐结合态铀提取结果的可重复性最好(RSD为2.6%),其次为硫化物及有机物结合态铀(RSD为4.0%)、结晶态铀(RSD为6.0%)和铁锰氧化物结合态铀(RSD为6.1%),可交换离子态铀提取结果的可重复性最差(RSD为26%)。碳酸盐结合态铀与结晶态铀之比,可以用于反映地下铀矿的存在概率。  相似文献   

16.
Sediment samples were collected from six springs draining the karst aquifer at Fort Campbell, Kentucky/Tennessee. These were analyzed by ICP-MS following an extraction procedure that separates the metals into exchangeable, carbonate, oxide, organic and residual fractions. Aluminum and iron are primarily present in the residual fraction while manganese may be dominantly in either the oxide or carbonate fraction. The redox-sensitive metals (Fe and Mn) have the greatest fractional distribution in the spring with the thickest sediments. Trace metals detected include Cr, Cd, Ni, Pb, and Zn in the range of a few to 200 mg/kg. In Beaver Spring, nickel is distributed between the exchangeable, carbonate and organic fractions, while in Gordon Spring, nickel is largely residual. Chromium is almost entirely associated with the organic fraction in Beaver Spring while it is largely residual in Gordon Spring.  相似文献   

17.
The species of Cu, Pb, Zn, Cd and Cr in sediments of the Taihu Lake, China, have been analyzed using the sequential chemical extraction method. Variations in the chemical fractions of these metals and their geographic distributions have also been studied. For all five metals, the residual fraction is highest but the exchangeable fraction is lowest among all the fractions. Compared to other metals, Cd has the highest percentage in the exchangeable fraction, and Cr is associated mainly with the residual fraction. Cu in the organic fraction and Pb in the Fe-Mn fraction are the important species, whereas the lowest percentages are found for Cd in the organic fraction, Cu in the Fe-Mn oxide fraction and Pb in the carbonate fraction. With respect to spatial differences, the total contents in the non-residual fractions of the metals in bay sediments are found to be higher than those in other sediments. The fractions of Cd, Cu and Cr showed significant variations in different regions. The fractions of Pb and Zn, however, did not show significant variations in spatial distribution, suggesting different amounts and different paths of anthropogenic input for the metals. Comparisons of the metal speciation indicated that Cd might be the most bioavailable metal, followed by Pb.  相似文献   

18.
Total concentrations of chemical elements in soils may not be enough to understand the mobility and bioavailability of the elements. It is important to characterise the degree of association of chemical elements in different physical and chemical phases of soil. Another geochemical characterisation methodology is to apply sequential selective chemical extraction techniques. A seven-step sequential extraction procedure was used to investigate the mobility and retention behaviour of Al, Fe, Mn, Cu, Zn, Pb, Cr, Co, Ni, Mo, Cd, Bi, Sn, W, Ag, As and U in specific physical–chemical and mineral phases in mine tailings and soils in the surroundings of the abandoned Ervedosa mine. The soil geochemical data show anomalies associated with mineralised veins or influenced by mining. Beyond the tailings, the highest recorded concentrations for most elements are in soils situated in mineralised areas or under the influence of tailings. The application of principal components analysis allowed recognition of (a) element associations according to their geochemical behaviour and (b) distinction between samples representing local geochemical background and samples representing contamination. Some metal cations (Mn, Cd, Cu, Zn, Co, Cr, Ni) showed important enrichment in the most mobilisable and bioavailable (i.e., water-soluble and exchangeable) fractions due likely to the acidic conditions in the area. In contrast, oxy-anions such as Mo and As showed lower mobility because of adsorption to Fe oxy-hydroxides. The residual fraction comprised largest proportions of Sn and Al and to a lesser extent Zn, Pb, Ni, Cr, Bi, W, and Ag, which are also present at low concentrations in the bioavailable fractions. The elements in secondary mineral phases (mainly Fe, Mn, Cu, Zn, Cd, Pb, W, Bi, Mo, Cr, Ni, Co, As and U) as well as in organic matter and sulphides are temporarily withheld, suggesting that they may be released to the environment by changes in physico-chemical conditions.  相似文献   

19.
Trace levels of chalcophile elements that form volatile sulfide minerals are determined in stream sediments and in the nonmagnetic fraction of a heavy-mineral concentrate of stream sediments by a carrier distillation emission spectrographic method. Photographically recorded spectra of samples are visually compared with those of synthetic standards for the two sample types. Rock and soil samples may also be analyzed by comparison with the stream-sediment standards. A gallium oxide spectrochemical carrier/buffer enhances the early emission of the volatile elements.Detection limits in parts per million attained are: Sb 5, As 20, Bi 0.1, Cd 1, Cu 1, Pb 2, Ag 0.1, Zn 2, and Sn 0.1. A comparison with other methods of analysis, total-burn emission and atomic absorption spectroscopy, shows good correlation for standard reference for materials and samples from a variety of geologic terranes.  相似文献   

20.
山西临汾-运城盆地土壤中As含量的变化规律   总被引：2，自引：0，他引：2  
通过对临汾-运城盆地表层和深层土壤中As含量变化规律的研究,发现表层土壤的As含量稍高于全国土壤的背景值,不同相态的含量差异较大。土壤pH、磁化率、有机质、粘粒含量等理化性质对不同形态的As有着不同程度的影响：研究区水溶态的As受土壤pH值的控制,腐殖质结合态的As与有机质呈明显的正相关关系,磁化率、粘粒含量与土壤As的含量都有明显的正相关关系。研究结果表明,As与Fe、Mn、Cu、Zn、Mg、K、F等元素的相关性非常显著,说明研究区表层土壤中的As主要是自然成因的。进一步的回归分析表明,土壤的As含量随着铁氧化物、氢氧化物和硫化物含量的增加而增加。研究区土壤As的纵向分布特点是中层多、上下层少,这可能与研究区As的污染状况、土壤的碱性环境、植物的吸收作用、磷肥的施用等因素有关。  相似文献   

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